Organic photosensitive devices using subphthalocyanine compounds

ABSTRACT

An organic photosensitive optoelectronic device, having a donor-acceptor heterojunction of a donor-like material and an acceptor-like material and methods of making such devices is provided. At least one of the donor-like material and the acceptor-like material includes a subphthalocyanine, a subporphyrin, and/or a subporphyrazine compound; and/or the device optionally has at least one of a blocking layer or a charge transport layer, where the blocking layer and/or the charge transport layer includes a subphthalocyanine, a subporphyrin, and/or a subporphyrazine compound.

UNITED STATES GOVERNMENT RIGHTS

This invention was made with U.S. Government support under Contract No.XAT-5-33636-03, awarded by the U.S. Department of Energy, NationalRenewable Energy Laboratory. The government has certain rights in thisinvention.

JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a jointuniversity-corporation research agreement: Princeton University, TheUniversity of Southern California, The University of Michigan, andGlobal Photonic Energy Corporation. The agreement was in effect on andbefore the date the claimed invention was made, and the claimedinvention was made as a result of activities undertaken within the scopeof the agreement.

FIELD OF THE INVENTION

The present invention generally relates to organic photosensitiveoptoelectronic devices. More specifically, it is directed to organicphotosensitive optoelectronic devices having a donor acceptorheterojunction, comprising a donor-like material and an acceptor-likematerial, at least one of the donor-like material and the acceptor-likematerial comprises a subphthalocyanine, subporphyrin, and/orsubporphyrazine material; and/or the device optionally comprises atleast one of a blocking layer or a charge transport layer, wherein theblocking layer and/or the charge transport layer comprises asubphthalocyanine, a subporphyrin, and/or a subporphyrazine compound.

BACKGROUND OF THE INVENTION

Optoelectronic devices rely on the optical and electronic properties ofmaterials to either produce or detect electromagnetic radiationelectronically or to generate electricity from ambient electromagneticradiation.

Photosensitive optoelectronic devices convert electromagnetic radiationinto an electrical signal or electricity. Solar cells, also calledphotovoltaic (“PV”) devices, are a type of photosensitive optoelectronicdevice that is specifically used to generate electrical power.Photoconductor cells are a type of photosensitive optoelectronic devicethat are used in conjunction with signal detection circuitry whichmonitors the resistance of the device to detect changes due to absorbedlight. Photodetectors, which may receive an applied bias voltage, are atype of photosensitive optoelectronic device that are used inconjunction with current detecting circuits which measures the currentgenerated when the photodetector is exposed to electromagneticradiation.

These three classes of photosensitive optoelectronic devices may bedistinguished according to whether a rectifying junction as definedbelow is present and also according to whether the device is operatedwith an external applied voltage, also known as a bias or bias voltage.A photoconductor cell does not have a rectifying junction and isnormally operated with a bias. A PV device has at least one rectifyingjunction and is operated with no bias. A photodetector has at least onerectifying junction and is usually but not always operated with a bias.

As used herein, the term “rectifying” denotes, inter alia, that aninterface has an asymmetric conduction characteristic, i.e., theinterface supports electronic charge transport preferably in onedirection. The term “semiconductor” denotes materials which can conductelectricity when charge carriers are induced by thermal orelectromagnetic excitation. The term “photoconductive” generally relatesto the process in which electromagnetic radiant energy is absorbed andthereby converted to excitation energy of electric charge carriers sothat the carriers can conduct (i.e., transport) electric charge in amaterial. The term “photoconductive material” refers to semiconductormaterials which are utilized for their property of absorbingelectromagnetic radiation to generate electric charge carriers. As usedherein, “top” means furthest away from the substrate, while “bottom”means closest to the substrate. There may be intervening layers, unlessit is specified that the first layer is “in physical contact with” thesecond layer.

When electromagnetic radiation of an appropriate energy is incident uponan organic semiconductor material, a photon can be absorbed to producean excited molecular state. In organic photoconductive materials, thegenerated molecular state is generally believed to be an “exciton,”i.e., an electron-hole pair in a bound state which is transported as aquasi-particle. An exciton can have an appreciable life-time beforegeminate recombination (“quenching”), which refers to the originalelectron and hole recombining with each other (as opposed torecombination with holes or electrons from other pairs). To produce aphotocurrent, the electron-hole forming the exciton is typicallyseparated at a rectifying junction.

In the case of photosensitive devices, the rectifying junction isreferred to as a photovoltaic heterojunction. Types of organicphotovoltaic heterojunctions include a donor-acceptor heterojunctionformed at an interface of a donor material and an acceptor material, anda Schottky-barrier heterojunction formed at the interface of aphotoconductive material and a metal.

FIG. 1 is an energy-level diagram illustrating an example donor-acceptorheterojunction. In the context of organic materials, the terms “donor”and “acceptor” refer to the relative positions of the Highest OccupiedMolecular Orbital (“HOMO”) and Lowest Unoccupied Molecular Orbital(“LUMO”) energy levels of two contacting but different organicmaterials. If the LUMO energy level of one material in contact withanother is lower, then that material is an acceptor. Otherwise it is adonor. It is energetically favorable, in the absence of an externalbias, for electrons at a donor-acceptor junction to move into theacceptor material.

As used herein, a first HOMO or LUMO energy level is “greater than” or“higher than” a second HOMO or LUMO energy level if the first energylevel is closer to the vacuum energy level 10. A higher HOMO energylevel corresponds to an ionization potential (“IP”) having a smallerabsolute energy relative to a vacuum level. Similarly, a higher LUMOenergy level corresponds to an electron affinity (“EA”) having a smallerabsolute energy relative to vacuum level. On a conventional energy leveldiagram, with the vacuum level at the top, the LUMO energy level of amaterial is higher than the HOMO energy level of the same material.

After absorption of a photon 6 in the donor 152 or the acceptor 154creates an exciton 8, the exciton 8 disassociates at the rectifyinginterface. The donor 152 transports the hole (open circle) and theacceptor 154 transports the electron (dark circle).

A significant property in organic semiconductors is carrier mobility.Mobility measures the ease with which a charge carrier can move througha conducting material in response to an electric field. In the contextof organic photosensitive devices, a material that conductspreferentially by electrons due to a high electron mobility may bereferred to as an electron transport material. A material that conductspreferentially by holes due to a high hole mobility may be referred toas a hole transport material. A layer that conducts preferentially byelectrons, due to mobility and/or position in the device, may bereferred to as an electron transport layer (“ETL”). A layer thatconducts preferentially by holes, due to mobility and/or position in thedevice, may be referred to as a hole transport layer (“HTL”).Preferably, but not necessarily, an acceptor material is an electrontransport material and a donor material is a hole transport material.

How to pair two organic photoconductive materials to serve as a donorand an acceptor in a photovoltaic heterojunction based upon carriermobilities and relative HOMO and LUMO levels is well known in the art,and is not addressed here.

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule.” In general, asmall molecule has a defined chemical formula with a molecular weightthat is the same from molecule to molecule, whereas a polymer has adefined chemical formula with a molecular weight that may vary frommolecule to molecule. As used herein, “organic” includes metal complexesof hydrocarbyl and heteroatom-substituted hydrocarbyl ligands.

Padinger, et al., Adv. Funct. Mater., 2003, 13, 85-88, reportedphotovoltaic cells, comprising polymer-fullerene heterojunctions thatreportedly had power conversion efficiencies averaging 3 to 4 percent.Efficiencies approaching 5 percent were reportedly also obtained throughvariations in the processing techniques. Efficiencies as high as 4percent under 4 suns simulated AM1.5G illumination in adouble-heterostructure copper phthalocyanine (CuPc)/C₆₀ thin film cellwith Ag as the metal cathode have been reported by Xue, et al., Appl.Phys. Lett., 2004, 84, 3013-3015. PV cells, enhanced by stacking twocells in series, and yielding efficiencies exceeding 5.5 percent havealso been reported. Xue, et al., Appl. Phys. Lett. 2004, 85, 5757-5759.

For additional background explanation and description of the state ofthe art for organic photosensitive devices, including their generalconstruction, characteristics, materials, and features, U.S. Pat. No.6,657,378 to Forrest et al., U.S. Pat. No. 6,580,027 to Forrest et al.,and U.S. Pat. No. 6,352,777 to Bulovic et al. are incorporated herein byreference.

Further improvements in the efficiency of organic photosensitive deviceswould clearly be advantageous. The present invention provides suchorganic photosensitive devices with improved efficiency.

SUMMARY OF THE INVENTION

The invention is directed to organic photosensitive optoelectronicdevices, comprising an anode, a cathode, and a donor-acceptorheterojunction between the anode and the cathode. The heterojunctioncomprises a donor-like material and an acceptor-like material, where atleast one of the donor-like material and the acceptor-like materialcomprises a subphthalocyanine, a subporphyrin, and/or a subporphyrazinecompound; and/or the device optionally comprises at least one of ablocking layer or a charge transport layer, wherein the blocking layerand/or the charge transport layer comprises a subphthalocyanine, asubporphyrin, and/or a subporphyrazine compound.

The invention is further directed to a method of preparing aheterojunction, where the heterojunction comprises a donor-like materialand an acceptor-like material. The method comprises selecting adonor-like material having a LUMO and a HOMO, selecting asubphthalocyanine, a subporphyrin, or a subporphyrazine material,substituted with at least one electron withdrawing or electron donatingsubstituent group, wherein the substituent group modulates thesubphthalocyanine, subporphyrin, or subporphyrazine material LUMO andHOMO, such that the subphthalocyanine, subporphyrin, or subporphyrazinematerial is an acceptor-like material for the donor-like material, andforming a heterojunction from the donor-like and acceptor likematerials; or selecting an acceptor-like material, selecting asubphthalocyanine, a subporphyrin, or a subporphyrazine material,substituted with at least one electron withdrawing or electron donatingsubstituent group, wherein the substituent group modulates thesubphthalocyanine, subporphyrin, or subporphyrazine material LUMO andHOMO, such that the subphthalocyanine, subporphyrin, or subporphyrazinematerial is a donor-like material for the acceptor-like material, andforming a heterojunction from the donor-like and acceptor likematerials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an energy level diagram illustrating a donor-acceptorheterojunction;

FIG. 2 illustrates an organic photosensitive device including adonor-acceptor heterojunction;

FIG. 3 illustrates a donor-acceptor bilayer forming a planarheterojunction;

FIG. 4 illustrates a hybrid heterojunction including a mixedheterojunction between a donor layer and an acceptor layer;

FIG. 5 illustrates a bulk heterojunction;

FIG. 6 illustrates an organic photosensitive device including aSchottky-barrier heterojunction;

FIG. 7 illustrates tandem photosensitive cells in series;

FIG. 8 illustrates tandem photosensitive cells in parallel;

FIG. 9 illustrates a schematic energy level diagram for devices withCuPc and SubPc donor layers;

FIG. 10 illustrates absorbance spectra of stacked CuPc (200 Å)/C₆₀ (400Å)/BCP (100 Å) films on quartz and of SubPc_(BCl) (130 Å)/C₆₀ (325Å)/BCP (100 Å) films on quartz;

FIG. 11 illustrates the use of a subphthalocyanine compound as anacceptor-like material;

FIG. 12 illustrates J-V characteristics of ITO/CuPc (200 Å)/C₆₀ (400Å)/BCP (100 Å)/Al (1000 Å) and ITO/SubPc (130 Å)/C₆₀ (325 Å)/BCP (100Å)/Al (1000 Å) under 1 sun AM 1.5G simulated illumination and in thedark;

FIG. 13 illustrates J-V characteristics of an ITO/SubPc_(BCl) (130Å)/C₆₀ (325 Å)/BCP (100 Å)/Al (1000 Å) device (SubPc4) under AM1.5Gsimulated solar illumination at 1-5 suns; and

FIG. 14 illustrates J-V characteristics of ITO/CuPc (200 Å)/SubPc (130Å)/BCP (100 Å)/Al (1000 Å) under 1 sun AM1.5G simulated illumination andin the dark.

The figures are not necessarily drawn to scale.

DETAILED DESCRIPTION

An organic photosensitive device comprises at least one photoactiveregion in which light is absorbed to form an exciton, which maysubsequently dissociate into an electron and a hole. FIG. 2 shows anexample of an organic photosensitive optoelectronic device 100 in whichthe photoactive region 150 comprises a donor-acceptor heterojunction.The “photoactive region” is a portion of a photosensitive device thatabsorbs electromagnetic radiation to generate excitons that maydissociate in order to generate an electrical current. Device 100comprises an anode 120, an anode smoothing layer 122, a donor 152, anacceptor 154, an exciton blocking layer (“EBL”) 156, and a cathode 170,over a substrate 110.

Examples of EBL 156 are described in U.S. Pat. No. 6,451,415 to Forrestet al., which is incorporated herein by reference for its disclosurerelated to EBLs. Additional background explanation of EBLs may also befound in Peumans et al., “Efficient photon harvesting at high opticalintensities in ultra-thin organic double-heterostructure photovoltaicdiodes,” Applied Physics Letters 76, 2650-52 (2000). EBLs reducequenching by preventing excitons from migrating out of the donor and/oracceptor materials.

The terms “electrode” and “contact” are used interchangeably herein torefer to a layer that provides a medium for delivering photo-generatedcurrent to an external circuit or providing a bias current or voltage tothe device. As illustrated in FIG. 2, anode 120 and cathode 170 areexamples. Electrodes may be composed of metals or “metal substitutes.”Herein the term “metal” is used to embrace both materials composed of anelementally pure metal, and also metal alloys which are materialscomposed of two or more elementally pure metals. The term “metalsubstitute” refers to a material that is not a metal within the normaldefinition, but which has the metal-like properties such asconductivity, such as doped wide-bandgap semiconductors, degeneratesemiconductors, conducting oxides, and conductive polymers. Electrodesmay comprise a single layer or multiple layers (a “compound” electrode),may be transparent, semi-transparent, or opaque. Examples of electrodesand electrode materials include those disclosed in U.S. Pat. No.6,352,777 to Bulovic et al., and U.S. Pat. No. 6,420,031, toParthasarathy, et al., each incorporated herein by reference fordisclosure of these respective features. As used herein, a layer is saidto be “transparent” if it transmits at least 50 percent of the ambientelectromagnetic radiation in a relevant wavelength.

The substrate 110 may be any suitable substrate that provides desiredstructural properties. The substrate may be flexible or rigid, planar ornon-planar. The substrate may be transparent, translucent, or opaque.Rigid plastics and glass are examples of preferred rigid substratematerials. Flexible plastics and metal foils are examples of preferredflexible substrate materials.

An anode-smoothing layer 122 may be situated between the anode layer 120and the donor layer 152. Anode-smoothing layers are described in U.S.Pat. No. 6,657,378 to Forrest et al., incorporated herein by referencefor its disclosure related to this feature.

In FIG. 2, the photoactive region 150 comprises the donor material 152and the acceptor material 154. Organic materials for use in thephotoactive region may include organometallic compounds, includingcyclometallated organometallic compounds. The term “organometallic” asused herein is as generally understood by one of ordinary skill in theart and as given, for example, in Chapter 13 of “Inorganic Chemistry”(2nd Edition) by Gary L. Miessler and Donald A. Tarr, Prentice Hall(1999).

Organic layers may be fabricated using vacuum deposition, spin coating,organic vapor-phase deposition, inkjet printing, and other methods knownin the art.

Examples of various types of donor-acceptor heterojunctions are shown inFIGS. 3-5. FIG. 3 illustrates a donor-acceptor bilayer forming a planarheterojunction. FIG. 4 illustrates a hybrid heterojunction including amixed heterojunction 153 comprising a mixture of donor and acceptormaterials. FIG. 5 illustrates an idealized “bulk” heterojunction. A bulkheterojunction, in the ideal photocurrent case, has a single continuousinterface between the donor material 252 and the acceptor material 254,although multiple interfaces typically exist in actual devices. Mixedand bulk heterojunctions can have multiple donor-acceptor interfaces asa result of having plural domains of material. Domains that aresurrounded by the opposite-type material (e.g., a domain of donormaterial surrounded by acceptor material) may be electrically isolated,such that these domains do not contribute to photocurrent. Other domainsmay be connected by percolation pathways (continuous photocurrentpathways), such that these other domains may contribute to photocurrent.The distinction between a mixed and a bulk heterojunction lies indegrees of phase separation between donor and acceptor materials. In amixed heterojunction, there is very little or no phase separation (thedomains are very small, e.g., less than a few nanometers), whereas in abulk heterojunction, there is significant phase separation (e.g.,forming domains with sizes of a few nanometers to 100 nm).

Small-molecule mixed heterojunctions may be formed, for example, byco-deposition of the donor and acceptor materials using vacuumdeposition or vapor deposition. Small-molecule bulk heterojunctions maybe formed, for example, by controlled growth, co-deposition withpost-deposition annealing, or solution processing. Polymer mixed or bulkheterojunctions may be formed, for example, by solution processing ofpolymer blends of donor and acceptor materials.

If a photoactive region includes a mixed layer (153) or bulk layers(252, 254) and one or both of the donor (152) and acceptor layers (154),the photoactive region is said to include a “hybrid” heterojunction. Thearrangement of layers in FIG. 4 is an example. For additionalexplanation of hybrid heterojunctions, Published U.S. Patent Application2005/0224113 A1, entitled “High efficiency organic photovoltaic cellsemploying hybridized mixed-planar heterojunctions” by Jiangeng Xue etal., published Oct. 13, 2005, is hereby incorporated by reference.

In general, planar heterojunctions have good carrier conduction, butpoor exciton dissociation; a mixed layer has poor carrier conduction andgood exciton dissociation, and a bulk heterojunction has good carrierconduction and good exciton dissociation, but may experience chargebuild-up at the end of the material “cul-de-sacs,” lowering efficiency.Unless otherwise stated, planar, mixed, bulk, and hybrid heterojunctionsmay be used interchangeably as donor-acceptor heterojunctions throughoutthe embodiments disclosed herein.

FIG. 6 shows an example of an organic photosensitive optoelectronicdevice 300 in which the photoactive region 350 is part of aSchottky-barrier heterojunction. Device 300 comprises a transparentcontact 320, a photoactive region 350 comprising an organicphotoconductive material 358, and a Schottky contact 370. The Schottkycontact 370 is typically formed as a metal layer. If the photoconductivelayer 358 is an ETL, a high work function metal such as gold may beused, whereas if the photoconductive layer is an HTL, a low workfunction metal such as aluminum, magnesium, or indium may be used. In aSchottky-barrier cell, a built-in electric field associated with theSchottky barrier pulls the electron and hole in an exciton apart.Generally, this field-assisted exciton dissociation is not as efficientas the disassociation at a donor-acceptor interface.

The devices as illustrated may be connected to an element 190. If thedevice is a photovoltaic device, element 190 is a resistive load whichconsumes or stores power. If the device is a photodetector, element 190is a current detecting circuit which measures the current generated whenthe photodetector is exposed to light, and which may apply a bias to thedevice (as described for example in Published U.S. Patent Application2005-0110007 A1, published May 26, 2005 to Forrest et al.). If therectifying junction is eliminated from the device (e.g., using a singlephotoconductive material as the photoactive region), the resultingstructures may be used as a photoconductor cell, in which case theelement 190 is a signal detection circuit to monitor changes inresistance across the device due to the absorption of light. Unlessotherwise stated, each of these arrangements and modifications may beused for the devices in each of the drawings and embodiments disclosedherein.

An organic photosensitive optoelectronic device may also comprisetransparent charge transfer layers, electrodes, or charge recombinationzones. A charge transfer layer may be organic or inorganic, and may ormay not be photoconductively active. A charge transfer layer is similarto an electrode, but does not have an electrical connection external tothe device and only delivers charge carriers from one subsection of anoptoelectronic device to the adjacent subsection. A charge recombinationzone is similar to a charge transfer layer, but allows for therecombination of electrons and holes between adjacent subsections of anoptoelectronic device. A charge recombination zone may includesemi-transparent metal or metal substitute recombination centerscomprising nanoclusters, nanoparticles, and/or nanorods, as describedfor example in U.S. Pat. No. 6,657,378 to Forrest et al.; Published U.S.Patent Application 2006-0032529 A1, entitled “Organic PhotosensitiveDevices” by Rand et al., published Feb. 16, 2006; and Published U.S.Patent Application 2006-0027802 A1, entitled “Stacked OrganicPhotosensitive Devices” by Forrest et al., published Feb. 9, 2006; eachincorporated herein by reference for its disclosure of recombinationzone materials and structures. A charge recombination zone may or maynot include a transparent matrix layer in which the recombinationcenters are embedded. A charge transfer layer, electrode, or chargerecombination zone may serve as a cathode and/or an anode of subsectionsof the optoelectronic device. An electrode or charge transfer layer mayserve as a Schottky contact.

FIGS. 7 and 8 illustrate examples of tandem devices including suchtransparent charge transfer layers, electrodes, and charge recombinationzones. In device 400, in FIG. 7, photoactive regions 150 and 150′ arestacked electrically in series with an intervening conductive region460. As illustrated without external electrical connections, interveningconductive region 460 may be a charge recombination zone or may be acharge transfer layer. As a recombination zone, region 460 comprisesrecombination centers 461 with or without a transparent matrix layer. Ifthere is no matrix layer, the arrangement of material forming the zonemay not be continuous across the region 460. Device 500, in FIG. 8,illustrates photoactive regions 150 and 150′ stacked electrically inparallel, with the top cell being in an inverted configuration (i.e.,cathode-down). In each of FIGS. 7 and 8, the photoactive regions 150 and150′ and blocking layers 156 and 156′ may be formed out of the samerespective materials, or different materials, depending upon theapplication. Likewise, photoactive regions 150 and 150′ may be a sametype (i.e., planar, mixed, bulk, hybrid) of heterojunction, or may be ofdifferent types.

In each of the devices described above, layers may be omitted, such asthe exciton blocking layers. Other layers may be added, such asreflective layers or additional photoactive regions. The order of layersmay be altered or inverted. A concentrator or trapping configuration maybe employed to increase efficiency, as disclosed, for example in U.S.Pat. No. 6,333,458 to Forrest et al. and U.S. Pat. No. 6,440,769 toPeumans et al., which are incorporated herein by reference. Coatings maybe used to focus optical energy into desired regions of a device, asdisclosed, for example in Published US Patent Application No.2005-0266218 A1, entitled “A periodic dielectric multilayer stack” byPeumans et al., published Dec. 1, 2005, which is incorporated herein byreference. In the tandem devices, transparent insulative layers may beformed between cells, with the electrical connection between the cellsbeing provided via electrodes. In addition, in the tandem devices, oneor more of the photoactive regions may be a Schottky-barrierheterojunction instead of a donor-acceptor heterojunction. Arrangementsother than those specifically described may be used.

As used herein, the terms “subphthalocyanine compounds” and “SubPc”refer to compounds of formula

where R₁ to R₁₂, M, and X are each selected independently. R₁ to R₁₂ maybe electron withdrawing or electron donating, and are preferablyindependently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl (e.g., SC₈H₁₇) thioaryl(e.g., SC₆H₅), arylsulfonyl (e.g. SO₂C₆H₅), alkylsufonyl (e.g.,SO₂C₈H₁₇), amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, nitro, and related electron accepting and donating groups, wellknown to those skilled in the art. In addition, any two adjacent Rgroups (R₁ to R₁₂) can be part of a fused aromatic (includingheterocyclic) ring, M is boron or a divalent metal, such as Be or Mg, ora trivalent metal, such as Al or Ga, and X is an anionic group, such ashalide (fluoride, chloride, bromide, or iodide), alkoxy, phenoxy,hydroxy, aryl, phenyl, and OCOCR₁₃R₁₄R₁₅, where R₁₃, R₁₄, and R₁₅ may beelectron withdrawing or electron donating, and are preferablyindependently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl (e.g., SC₈H₁₇) thioaryl(e.g., SC₆H₅), arylsulfonyl (e.g. SO₂C₆H₅), alkylsufonyl (e.g.,SO₂C₈H₁₇), amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, nitro, and related electron accepting and donating groups, wellknown to those skilled in the art. Preferably, M is B or Al, and, mostpreferably, M is B. Any of R₁ to R₁₂ that are adjacent can be part of afused aliphatic or aromatic ring, where the ring may contain one or moreatoms other than carbon, such as N, O, and S.

As used herein, “SubPc_(BCl)” refers to boron subphthalocyaninechloride, a SubPc compound in which M is B, X is Cl, and each of R₁ toR₁₂ is H. Subphthalocyanine compounds may be prepared using theprocesses disclosed by Geyer et al., Subphthalocyanines: Preparation,Reactivity and Physical Properties, Synthesis, September 1996, 1139-51,Rauschnabel et al., New Derivatives and Homologues of Subphthalocyanine,Tetrahedron Letters, 36, 1995, 1629-32, the contents of which areincorporated herein by reference in their entirety.

Also, as used herein, the terms “subporphyrin,” “subporphyrin compound,”and “SubPor compound” refer to compounds of formula

where R₁ to R₁₂, M, X, and Z are each selected independently, R₁ to R₁₂,M, and X are as defined above, and Z is N, CH, CR₁₆, where R₁₆ is may beelectron withdrawing or electron donating, and is preferablyindependently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl (e.g., SC₈H₁₇) thioaryl(e.g., SC₆H₅), arylsulfonyl (e.g. SO₂C₆H₅), alkylsufonyl (e.g.,SO₂C₈H₁₇), amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, nitro, and related electron accepting and donating groups, wellknown to those skilled in the art. Subporphyrin compounds are preferablyprepared using the synthesis disclosed by Inokuma et al.,Tribenzosubporphine: Synthesis and Characterization, Angew. Chem. Int.Ed., 2006, 45, 961-64, the contents of which are incorporated herein intheir entirety by reference.

As used herein, the terms “subporphyrazine” and “subporphyrazinecompounds” refer to compounds of formula:

where R₁ to R₆, M, X, and Z are each selected independently, R₁ to R₆,M, and X are as defined above, and Z is N, CH, CR₁₆, where R₁₆ is whereR₁₆ is may be electron withdrawing or electron donating, and ispreferably independently selected from the group consisting of H,straight, branched, or cyclic alkyl, halide, thioalkyl (e.g., SC₈H₁₇)thioaryl (e.g., SC₆H₅), arylsulfonyl (e.g., SO₂C₆H₅), alkylsufonyl(e.g., SO₂C₈H₁₇), amino, alkylamino, arylamino, hydroxy, alkoxy,acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl,sulfonyl, cyano, nitro, and related electron accepting and donatinggroups, well known to those skilled in the art. However, if any adjacentpairs of R₁ to R₆ are part of a fused aromatic ring system, the compoundis a subphthalocyanine or subporphyrin, not a subporphyrazine.Subporphyrazine compounds are preferably prepared using the synthesisdisclosed by Rodrigues-Morgade, et al., Synthesis, Characterization, andProperties of Subporphyrazines: A New Class of Nonplanar, AromaticMacrocycles with Absorption in the Green Region, Che. Euro. J., 2005,11, 354-360, the contents of which are incorporated herein in theirentirety by reference.

Examples of subphthalocyanine compounds useful in the invention include,but are not limited to

where R₁ to R₁₂, M, and X are as defined above.

Krempl et al., Synthesis 2000, 1705-8, the contents of which areincorporated herein by reference in their entirety, disclose reactinghexacyanotriphenylene,

with a phthalocyanine to prepare spherical phthalocyanine molecules,such as compounds having the following structure.

The same technique can be used to prepare oligomeric sheets of SubPc andSubPor compounds, such as a hexacyanotriphenylene SubPc_(BCl), havingthe following partial structure.

Where the SubPc oligomer is sufficiently large, i.e., comprising asufficient number of SubPc units, the oligomer will be substantiallyspherical. Similar subporphyrazine oligomeric sheets of can be preparedusing the same technique.

The invention is directed to organic photosensitive optoelectronicdevices, comprising an anode, a cathode, and a donor-acceptorheterojunction between the anode and the cathode. The heterojunctioncomprises a donor-like material and an acceptor-like material, and atleast one of the donor-like material and the acceptor-like materialcomprises a subphthalocyanine, subporphyrin, and/or subporphyrazinecompound; and/or the device optionally comprises at least one of ablocking layer or a charge transport layer, wherein the blocking layerand/or the charge transport layer comprises a subphthalocyanine, asubporphyrin, and/or a subporphyrazine compound. In accordance with theinvention, photosensitive optoelectronic devices in whichsubphthalocyanine, subporphyrin, and/or subporphyrazine compounds may beused as donor-like and/or acceptor-like materials include, but are notlimited to, solar cells, photodetectors, and photosensors.Heterojunctions useful in the devices of the invention include, but arenot limited to planar heterojunctions, mixed heterojunctions, bulkheterojunctions, and hybrid planar-mixed molecular heterojunctions.

A figure of merit for PV devices is the fill factor, FF, which isdefined in U.S. Pat. No. 6,451,415, the contents of which areincorporated herein in their entirety by reference, as:FF=(J _(max) ·V _(max))/(J _(SC) ·V _(OC))   (1)where J_(max) and V_(max) are the maximum current and voltage obtainablefrom the device, J_(SC) is the short-circuit current density, and V_(OC)is the open-circuit voltage. The fill factor, FF, is always less than 1,as J_(SC) and V_(OC) cannot be obtained simultaneously in actual use.However, as FF approaches 1, the series or internal resistance of thedevice decreases, and, thus, the device delivers a greater percentage ofthe product of J_(SC) and V_(OC) to the load under optimal conditions.

The power conversion efficiency of a PV device, η_(P), is a function ofthe V_(oc), J_(sc), and FF via:η_(P)=(J _(SC) ·V _(oc) ·FF)/P _(o)   (2)where P_(o) is the incident optical power. As FF is a function of theseries resistance, it typically has a value of from about 0.5 to about0.65 for small molecular weight organic PV devices. The value of J_(sc)is a function of the overlap between the absorption spectrum of theorganic donor-like and acceptor-like materials in the device and thesolar spectrum, as well as the magnitudes of the extinction coefficientsand the thicknesses of the absorbing layers. However, enhanced spectraloverlap is preferably provided without a significant loss in excitondiffusion length or in the charge transport properties of the materials.Typically, the value of V_(oc) is about 500 mV at 1 sun for aconventional CuPc/C₆₀ PV cell, which is significantly less than theenergy of the absorbed photon, i.e., about 2 eV. An increase in V_(oc)without a significant corresponding decrease in J_(sc) or FF wouldprovide a significant improvement in η_(P). However, prior to thepresent invention, it was difficult, if not impossible, to obtain asignificant increase in the value of V_(oc) without an accompanyingdecrease in J_(sc) and/or FF, limiting any improvement in η_(P).

Without being bound by theory, it is believed that the value of V_(oc)in an organic photosensitive optoelectronic device, such as an organicsolar cell, depends on the energy difference between the lowestunoccupied molecular orbital (LUMO) of the acceptor-like material andthe highest occupied molecular orbital (HOMO) of the donor-like materialat the heterointerface in a bilayer cell, referred to herein as theinterface gap, I_(g), as illustrated in FIG. 9. Preferably, in organicphotosensitive optoelectronic devices of the invention, a significantlygreater interface gap is attained with a subphthalocyanine,subporphyrin, and/or subporphyrazine material, particularly when thesubphthalocyanine, subporphyrin, and/or subporphyrazine compound is usedas the donor-like material, than can be attained in devices using priorart materials. For example, a double heterostructure SubPc_(BCl)/C₆₀thin-film cell has an I_(g) of 1.9 eV, compared to 1.5 eV for a CuPc/C₆₀cell. The value of V_(oc) of the SubPc_(BCl) cell is also increased byapproximately the same magnitude, indicating that the value of V_(oc)may be a function of I_(g).

Such a double heterojunction SubPc_(BCl)/C₆₀ thin-film PV cell providesat least about twice the V_(oc) and η_(P) of a conventional copperphthalocyanine (CuPc)/C₆₀ PV cell without a corresponding decrease inJ_(oc) and/or FF. The increased values of V_(oc) and η_(P) result froman increase in the value of I_(g), as a result of the increasedoxidation potential of the SubPc compound relative to CuPc.

Substitution of the peripheral substituents on a subphthalocyanine,subporphyrin, or subporphyrazine compound changes the redox propertiesof the material, modulating the LUMO and HOMO energies of the complex.As the excited state is largely ligand based, in the π-system, the Rgroup directly affects the absorption and emission energies of asubphthalocyanine, subporphyrin, or subporphyrazine compound as well.Generally, electron withdrawing groups would be expected to stabilizethe HOMO and LUMO levels, lowering the absolute value of the reductionpotential (they typically fall at negative potentials relative to commonreferences), and increase the oxidation potential, thereby moving theHOMO and LUMO energies further from the vacuum level (in energy). Incontrast, electron donating groups would be generally expected todestabilize the HOMO and LUMO levels, shifting the HOMO and LUMO levelscloser to the vacuum level, relative to the analogous unsubstitutedmaterial. However, the HOMO and LUMO levels are not necessarily affectedequally. Physical properties published for boron subphthalocyaninechloride analogues with peripheral substitution and boronsubnaphthalocyanine chloride (SubNc) are provided in Table 1. TABLE 1 ΔE(singlet- to- red. ox. Peripheral R group Abs λ_(max (nm)) ε (10⁴ M⁻¹cm⁻¹) E_(S) (kJ/mol) φ_(F) τ_(S) (ns) E_(T) (kJ/mol) φ_(T) τ_(T) (μs)triplet) (V) (V) H 564 6.30 209 0.25 3.3 175 0.62 82 30-40 −1.05 1.04SubNc 663 7.94 0.22 2.5 130 0.68- 95 42 0.78 kJ/mol t-Butyl^(a) 570 5.01209 0.16 2.8 166 0.55 127 −1.11 0.98 NO₂ ^(a) 586 3.16 203 0.20 3.2 1540.49 109 −0.57 1.34 I^(a) 572 5.01 208 0.01 <0.5 169 0.77 56 −0.92 1.13SC₈H₁₇ ^(a) 586 3.16 202 0.25 2.8 173 0.62 130 −1.09 0.95 SO₂C₈H₁₇ ^(a)573 3.16 207 0.18 3.1 162 0.25 144 −0.70 1.27 p-tolythio^(b) 606 7.94195 0.24 2.9 164 0.69 157 −0.97 1.02 p-tolysulfonyl^(b) 591 3.98 2000.23 2.9 152 0.42 132 −0.78 1.29 F^(c) 570 5 to 8 <5 −0.53 1.50^(a)Trisubstituted in the meta position ^(b)Hexasubstituted^(c)Dodecasubstituted

Modulating the LUMO and HOMO energies allows the donor and acceptorenergies of subphthalocyanine and subporphyrin compounds to be tuned fora given application. As a result, in the organic photosensitiveoptoelectronic device devices of the invention, compounds can beutilized as at least one of the donor-like and the acceptor-likematerials by energy matching the subphthalocyanine, subporphyrin, and/orsubporphyrazine material with an acceptor-like or donor-like material,and tailoring I_(g) and V_(oc) for a specific application.

Without being bound by theory, it is also believed that the dipolemoment of a molecule may cause charge trapping by the dipole. Forexample, in boron subphthalocyanine chloride, which has an axialchlorine substituent, the dipole moment of the subphthalocyaninecompound may contribute to decreased charge transport and increasedseries resistance in thicker layers of the subphthalocyanine compound inan organic photosensitive optoelectronic device. The axial substituenthas negligible impact on the redox properties of the subphthalocyanineor subporphyrin material, as shown in Table 2 for SubPc compounds inwhich M is B, and each of R₁ to R₁₂ is H, indicating that X is not partof the π-system, and, thus, has only a second order effect on the HOMO,LUMO, and excited state energies through M. The axial substituent doesinfluence how subphthalocyanine, subporphyrin, and subporphyrazinecompounds pack in a film. However, appropriate substitution of the axialsubstituent that decreases the dipole moment of a subphthalocyanine,subporphyrin, or subporphyrazine compound, and is expected to increasethe charge transport rate, due to a lower level of dipolar chargetrapping. Axial groups that are less electron withdrawing will generallyprovide a subphthalocyanine, subporphyrin, or subporphyrazine complexhaving a lower dipole moment. Increased charge transport in thesubphthalocyanine, subporphyrin, or subporphyrazine material allows theuse of thicker subphthalocyanine, subporphyrin, and/or subporphyrazinelayers in organic photosensitive optoelectronic devices. In PV cells,thicker subphthalocyanine, subporphyrin, and/or subporphyrazine layerswill result in increased J_(sc) and η_(P). In addition, substitution atthe peripheral or axial positions may also affect the packing of theSubPc in thin films, and subsequently affect the transport properties ofthe film. TABLE 2 Oxidation Potential Reduction Potential X (V) (V) Cl0.69 −1.40 OEt 0.71 −1.46 O-tert-butyl 0.58 −1.46

A lower dipole moment also decreases the likelihood of crystallizationof the complex, which can have a deleterious effect on the performanceof an organic photosensitive optoelectronic device, when the device isfabricated with a largely amorphous film. A crystalline film isadvantageous. However, crystallization after a device is fabricated willresult in a decrease in at least one of the performance or lifetime ofthe device, and a high dipole moment facilitates the crystallization.

While CuPc is a planar compound with an 18 π-electron phthalocyaninemacrocycle, unsubstituted subphthalocyanine and subporphyrin compoundscomprise three fused aromatic rings centered on a trivalent core, suchas boron or a divalent or trivalent metal. The resulting 14 π-electronaromatic macrocycle has a non-planar, cone-shaped structure with atetrahedral boron or a divalent or trivalent metal center out of planeof the aromatic ligand, and packs in a number of different orientations,depending on the deposition conditions. As will be understood by thoseskilled in the art, the addition of fused aromatic rings to the rings ofthe aromatic macrocycle will increase the number of electrons in theπ-system of the complex. Extending the π-system will result indelocalization, making it behave similarly to a subphthalocyanine orsubporphyrin compound substituted with an electron withdrawing group.That is, extending the π-system would be expected to lower the reductionpotential, and raise the oxidation potential, thereby lowering the HOMOand LUMO levels. For example, there is a red-shift in the absorptionspectrum for SubNc relative to SubPc_(BCl).

With strong absorption in the visible and extinction coefficientssimilar to CuPc, subphthalocyanine and subporphyrin compounds willfunction as a donor-like material. The first oxidation and reductionpotentials of SubPc_(BCl) are 0.69 V and −1.40 V, compared to aferrocene (Fc/Fc⁺) reference. Thus, C₆₀, having oxidation and reductionpotentials of 1.26 V and −1.06 V, compared to Fc/Fc⁺, is suitable as anacceptor material in a PV cell based on SubPc_(BCl). A comparison of theabsorbance spectra of stacked CuPc (200 Å)/C₆₀ (400 Å)/BCP (100 Å) filmson quartz and of SubPc_(BCl) (130 Å)/C₆₀ (325 Å)/BCP (100 Å) films onquartz is illustrated in FIG. 10. With appropriate substitution, theHOMO and LUMO energies of SubPc compounds can be adjusted for use asdonor-like materials in particular applications.

Similarly, a comparison of the HOMO and LUMO energies of CuPc and boronsubphthalocyanine chloride, as illustrated in FIG. 11, shows that thesubphthalocyanine compound is a suitable acceptor-like material withCuPc as a donor-like material. As with donor-like materials, withappropriate substitution, the HOMO and LUMO energies of SubPc compoundscan be adjusted for use as acceptor-like materials in particularapplications.

EXAMPLES

The following non-limiting examples are merely illustrative of thepreferred embodiments of the present invention, and are not to beconstrued as limiting the invention, the scope of which is defined bythe appended claims.

Boron subphthalocyanine chloride has been incorporated into an organicPV cell as donor-like material with C₆₀ as acceptor-like material andexhibits doubling of open circuit voltage and power conversionefficiency relative to a CuPc/C60 standard device.

Photovoltaic cells were grown on ITO-coated glass substrates that weresolvent cleaned, and treated in UV-ozone for 10 minutes immediatelyprior to loading into a high vacuum (˜3×10⁻⁶ Torr) chamber. The organicmaterials, SubPc (Aldrich), CuPc (Aldrich), C₆₀ (MTR Limited), and2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) (Aldrich) werepurified by sublimation prior to use. Metal cathode materials, Ag and Al(Alfa Aesar) were used as received. Materials were sequentially grown byvacuum thermal evaporation at the following rates: SubPc (1 Å/sec), C₆₀(2 Å/sec), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) (1.5Å/sec) and metals: 1000 Å thick Ag (4 Å/sec) or Al (2.5 Å/sec). Thecathode was evaporated through a shadow mask with 1 mm diameteropenings. Current-voltage (J-V) characteristics of PV cells weremeasured under simulated AM1.5G solar illumination (Oriel Instruments)using a Keithley 2420 3A Source Meter. Neutral density filters were usedto vary light intensity that was measured with a calibrated broadbandoptical power meter.

Conventional PV cell structures fabricated as controls were ITO/CuPc(200 Å)/C₆₀ (400 Å)/BCP (100 Å) with either a Ag (CuPc1) or Al cathode(CuPc2). The SubPc_(BCl) cells consisted of ITO/SubPc_(BCl) (200 Å)/C₆₀(400 Å)/BCP (100 Å) and a Ag (SubPc1) or Al (SubPc2) cathode. Thecurrent-density vs. voltage (J-V) characteristics were measured in thedark and under 1-5 suns AM1.5G simulated illumination uncorrected forsolar mismatch.

Although standard devices are made with 200 Å of CuPc, the SubPc devicesat 200 Å of SubPc showed poor performance. This is likely due to a highseries resistance which suggests that thinner donor layers are necessaryfor optimal device performance. Since SubPc absorbs at shorterwavelengths than CuPc, an optimal cell structure requires acorresponding decrease in C₆₀ thickness to ensure that the SubPc/C₆₀interface is located in a region where the short wavelength lightintensity is highest. Following this criterion, devices with thefollowing structure were fabricated: ITO/SubPc (130 Å)/C₆₀ (325 Å)/BCP(100 Å) with a Ag or Al cathode. As described above, organicphotosensitive devices of the present invention may be used to generateelectrical power from incident electromagnetic radiation (e.g.,photovoltaic devices) or may be used to detect incident electromagneticradiation (e.g., a photodetector or photoconductor cell).

Structure and photovoltaic data for devices illuminated under 1 sunAM1.5G simulated solar illumination and the J-V characteristics for thedevices at 1 sun are provided in Table 3. The V_(oc) of SubPc1 andSubPc2 is 150 mV higher than for CuPc cells, although both J_(sc) and FFare reduced, resulting in a reduced power efficiency. This is likely dueto a high series resistance which suggests that thinner donor layers arenecessary for optimal device performance. As SubPc_(BCl) absorbs atshorter wavelengths than CuPc, an optimal cell structure requires acorresponding decrease in C₆₀ thickness to ensure that theSubPc_(BCl)/C₆₀ interface is located in a region where the shortwavelength light intensity is highest. Following this criterion, adevice with the following structure was fabricated: ITO/SubPc_(BCL) (130Å)/C₆₀ (325 Å)/BCP (100 Å) with a Ag (SubPc3) or Al (SubPc4) cathode.TABLE 3 D/C₆₀ J_(sc) V_(oc) Cell (Å) M^(c) (mA cm⁻²) (V) FF η CuPc1200^(a)/400 Ag 4.13 0.43 0.61 1.2 CuPc2 200^(a)/400 Al 3.07 0.42 0.580.9 SubPc1 200^(b)/400 Ag 2.05 0.57 0.33 0.4 SubPc2 200^(b)/400 Al 1.830.58 0.36 0.4 SubPc3 130^(b)/325 Ag 3.61 0.98 0.41 1.7 SubPc4130^(b)/325 Al 3.36 0.97 0.57 2.1^(a)D = CuPc^(b)D = SubPc_(BCl)^(c)M is the cathode material

The J-V characteristics of SubPc4 and CuPc2 are shown in FIG. 12, withthe ITO/CuPc (200 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) represented bythe open circles and the ITO/SubPc (130 Å)/C₆₀ (325 Å)/BCP (100 Å)/Al(1000 Å) represented by filled circles under 1 sun AM1.5G simulatedillumination (solid) and in the dark (dashed). In this case, V_(oc) ofSubPc4 is more than double that of CuPc2, accompanied by a nearly 10percent increase in J_(sc). Although the SubPc absorption isblue-shifted relative to that of CuPc with a decreased absorbance atλ=700 nm, as illustrated in FIG. 10, this is compensated by theincreased absorbance at λ=590 nm, which is in a higher intensity regionof the solar spectrum. V_(oc) and FF of SubPc4 are nearly independent oflight intensity between 1 and 5 suns, as illustrated in FIG. 13, whilethe power conversion efficiency achieves a maximum value ofη_(P)=2.1±0.2 percent at 1 sun. The photovoltaic data for theITO/SubPc_(BCl) (130 Å)/C₆₀ (325 Å)/BCP (100 Å)/Al (1000 Å) device underAM1.5G simulated solar illumination at 1-5 suns is also set forth inTable 4. TABLE 4 J_(sc) V_(oc) Power (mA cm⁻²) (V) FF η 1 Sun 3.4 0.970.58 2.1 2 Sun 5.6 0.97 0.57 1.7 3 Sun 8.6 0.97 0.56 1.6 4 Sun 10.8 0.960.55 1.6 5 Sun 13.6 0.94 0.54 1.5

Photovoltaic data for devices having varying thicknesses of theSubPC_(BCl) layer in an ITO/SubPC_(BCl) (x Å)/C₆₀ (325 Å)/BCP (100 Å)/Al(1000 Å) device under AM1.5G simulated solar illumination at 1 sun areprovided in Table 5. TABLE 5 x J_(sc) V_(oc) (Å) (mA cm⁻²) (V) FF η 1003.07 0.81 0.48 1.3 115 2.63 0.88 0.60 1.5 130 3.36 0.97 0.57 2.1 2001.83 0.58 0.36 0.4

As illustrated in the energy level diagram for the CuPc and SubPc_(BCl)devices illustrated in FIG. 9, the SubPc_(BCl)/C₆₀ device has an I_(g)that is 400 meV greater than that of the CuPc/C₆₀ device, correlating toan increase of V_(oc) of approximately the same magnitude (550 mV). Thesignificant increase in V_(oc) is attributed to the smaller HOMO energyof SubPc_(BCl) and the subsequent increase in I_(g), showing that V_(oc)is dependent on I_(g). V_(oc) can be increased by series resistance,which may, in turn, depend on the presence of impurities or crystallinedisorder. The increase in V_(oc) is approximately 20 percent higher thanthat in I_(g), indicating that resistance is affecting V_(oc). Howeverthe high FF's indicate that resistance alone cannot account for theincreased V_(oc).

Varying the metal cathode has a minimal effect on V_(oc). However, CuPc1with a Ag cathode shows an increased J_(sc) and FF relative to theanalogous device with Al (CuPc2). It is unclear why such an effect onJ_(sc) and FF is observed, whereas V_(oc) is the same for both devices.Alternatively, for SubPc_(BCl), FF decreases for the Ag device (SubPc3)compared to the Al device (SubPc4). However, the SubPc_(BCl)/C₆₀ basedPV cells have more than twice the V_(oc) of conventional CuPc/C₆₀ cells,resulting in a more than doubling of the cell power conversionefficiency. By using a strongly absorbing donor material with a deepHOMO, I_(g), and, consequently, V_(oc), is increased without aconcomitant reduction in J_(sc). This indicates that I_(g) is likely adominant factor in determining V_(oc) in organic heterojunction cells.

The characteristics of a PV device using SubPc_(BCl) as an acceptor likematerial are described below. Photovoltaic cells were grown onITO-coated glass substrates that were solvent cleaned and treated inUV-ozone for 10 minutes immediately prior to loading into a high vacuum(˜3×10⁶ Torr) chamber. The organic materials, SubPc_(BCl) (Aldrich),CuPc (Aldrich), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)(Aldrich) were purified by sublimation prior to use. Metal cathodematerial, Al (Alfa Aesar) was used as received. Films were sequentiallygrown by vacuum thermal evaporation: CuPc (200 Å, 2 Å/sec), SubPc_(BCl)(130 Å, 1 Å/sec), BCP (100 Å, 1.5 Å/sec), and Al (1000 Å, 2.5 Å/sec).The cathode was evaporated through a shadow mask with 1 mm diameteropenings. Current-voltage (J-V) characteristics of PV cells weremeasured under simulated AM1.5G solar illumination (Oriel Instruments)using a Keithley 2420 3A Source Meter. Neutral density filters were usedto vary light intensity that was measured with a calibrated broadbandoptical power meter.

J-V characteristics at 1 sun are shown in FIG. 14 and listed in Table 6,demonstrating that devices of the invention may be prepared with SubPcmaterials that the materials act as acceptor-like materials. The lowpower conversion efficiency of the devices is a consequence of lowJ_(sc) and low FF. However, those values may be increased through deviceoptimization. TABLE 6 J_(sc) V_(oc) (mA cm⁻²) (V) FF η (%) 0.08 0.780.36 0.02

Specific examples of the invention are illustrated and/or describedherein. However, it will be appreciated that modifications andvariations of the invention are covered by the above teachings andwithin the purview of the appended claims without departing from thespirit and scope of the invention.

1. An organic photosensitive optoelectronic device, comprising an anode,a cathode, and a donor-acceptor heterojunction between the anode and thecathode, the heterojunction comprising a donor-like material and anacceptor-like material, wherein at least one of the donor-like materialand the acceptor-like material comprises a subphthalocyanine, asubporphyrin, and/or a subporphyrazine compound; and/or the deviceoptionally comprises at least one of a blocking layer or a chargetransport layer, wherein the blocking layer and/or the charge transportlayer comprises a subphthalocyanine, a subporphyrin, and/or asubporphyrazine compound.
 2. The organic photosensitive optoelectronicdevice of claim 1, wherein the donor-like material comprises asubphthalocyanine compound.
 3. The organic photosensitive optoelectronicdevice of claim 2, wherein the donor-like material is a boronsubphthalocyanine halide.
 4. The organic photosensitive optoelectronicdevice of claim 2, wherein the donor-like material is a boronsubphthalocyanine chloride.
 5. The organic photosensitive optoelectronicdevice of claim 2, wherein the subphthalocyanine compound is anoligomer.
 6. The organic photosensitive optoelectronic device of claim2, wherein the subphthalocyanine compound is of the formula

wherein R₁ to R₁₂, M, and X are each selected independently, at leastone of R₁ to R₁₂ is electron donating or electron withdrawing, and theremaining R₁ to R₁₂ groups are independently selected from the groupconsisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl,thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino,hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido,carboalkoxy, acyl, sulfonyl, cyano, and nitro, and any of R₁ to R₁₂ thatare adjacent can be part of a fused aliphatic or aromatic ring, whereinthe ring may contain one or more atoms other than carbon, M is boron, adivalent metal, or a trivalent metal, and X is an anionic group.
 7. Theorganic photosensitive optoelectronic device of claim 2, wherein thesubphthalocyanine compound is of the formula

wherein R₁ to R₁₂, M, and X are each selected independently, R₁ to R₁₂are independently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro, and any of R₁ to R₁₂ that are adjacent can be part ofa fused aliphatic or aromatic ring, wherein the ring may contain one ormore atoms other than carbon, M is boron, a divalent metal, or atrivalent metal, and X is an anionic group.
 8. The organicphotosensitive optoelectronic device of claim 7, wherein at least one ofR₁ to R₁₂ is selected from the group consisting of SC₈H₁₇, SC₆H₅,SO₂C₆H₅, and SO₂C₈H₁₇.
 9. The organic photosensitive optoelectronicdevice of claim 7, wherein M is selected from the group consisting of B,Be, Mg, Al, and Ga, and X is selected from the group consisting ofhalide, alkoxy, phenoxy, hydroxy, aryl, phenyl, and OCOCR₁₃R₁₄R₁₅,wherein R₁₃, R₁₄, and R₁₅ are independently selected from the groupconsisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl,thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino,hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido,carboalkoxy, acyl, sulfonyl, cyano, and nitro.
 10. The organicphotosensitive optoelectronic device of claim 9, wherein at least one ofR₁₃, R₁₄, and R₁₅ is selected from the group consisting of SC₈H₁₇,SC₆H₅, SO₂C₆H₅, and SO₂C₈H₁₇.
 11. The organic photosensitiveoptoelectronic device of claim 1, wherein the donor-like materialcomprises a subporphyrin compound.
 12. The organic photosensitiveoptoelectronic device of claim 11, wherein the subporphyrin compound isof the formula

wherein R₁ to R₁₂, M, and X are each selected independently, at leastone of R₁ to R₁₂ is electron donating or electron withdrawing, and theremaining R₁ to R₁₂ are independently selected from the group consistingof H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl,arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy,alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy,acyl, sulfonyl, cyano, and nitro, and any of R₁ to R₁₂ that are adjacentcan be part of a fused aliphatic or aromatic ring, wherein the ring maycontain one or more atoms other than carbon, M is boron, a divalentmetal, or a trivalent metal, X is an anionic group, and Z is N, CH,CR₁₆, wherein R₁₆ is selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro.
 13. The organic photosensitive optoelectronic deviceof claim 11, wherein the subporphyrin compound is of the formula

wherein R₁ to R₁₂, M, and X are each selected independently, R₁ to R₁₂are independently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro, and any of R₁ to R₁₂ that are adjacent can be part ofa fused aliphatic or aromatic ring, wherein the ring may contain one ormore atoms other than carbon, M is boron, a divalent metal, or atrivalent metal, X is an anionic group, and Z is N, CH, CR₁₆, whereinR₁₆ is selected from the group consisting of H, straight, branched, orcyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl,amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy,phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, andnitro.
 14. The organic photosensitive optoelectronic device of claim 13,wherein M is selected from the group consisting of B, Be, Mg, Al, andGa, and X is selected from the group consisting of halide, alkoxy,phenoxy, hydroxy, aryl, phenyl, and OCOCR₁₃R₁₄R₁₅, wherein R₁₃, R₁₄, andR₁₅ are independently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro.
 15. The organic photosensitive optoelectronic deviceof claim 11, wherein the subporphyrin compound is an oligomer.
 16. Theorganic photosensitive optoelectronic device of claim 1, wherein theacceptor-like material comprises a subphthalocyanine compound.
 17. Theorganic photosensitive optoelectronic device of claim 16, wherein theacceptor-like material is a boron subphthalocyanine halide.
 18. Theorganic photosensitive optoelectronic device of claim 16, wherein theacceptor-like material is a boron subphthalocyanine chloride.
 19. Theorganic photosensitive optoelectronic device of claim 16, wherein thesubphthalocyanine compound is of the formula

wherein R₁ to R₁₂, M, and X are each selected independently, at leastone of R₁ to R₁₂ is electron donating or electron withdrawing, and theremaining R₁ to R₁₂ are independently selected from the group consistingof may be electron withdrawing or electron donating, and are preferablyindependently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro, and any of R₁ to R₁₂ that are adjacent can be part ofa fused aliphatic or aromatic ring, wherein the ring may contain one ormore atoms other than carbon, M is boron, a divalent metal, or atrivalent metal, and X is an anionic group.
 20. The organicphotosensitive optoelectronic device of claim 16, wherein thesubphthalocyanine compound is of the formula

wherein R₁ to R₁₂, M, and X are each selected independently, R₁ to R₁₂are independently selected from the group consisting of may be electronwithdrawing or electron donating, and are preferably independentlyselected from the group consisting of H, straight, branched, or cyclicalkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino,alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl,carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro,and any of R₁ to R₁₂ that are adjacent can be part of a fused aliphaticor aromatic ring, wherein the ring may contain one or more atoms otherthan carbon, M is boron, a divalent metal, or a trivalent metal, and Xis an anionic group.
 21. The organic photosensitive optoelectronicdevice of claim 20, wherein M is selected from the group consisting ofB, Be, Mg, Al, and Ga, and X is X is selected from the group consistingof halide, alkoxy, phenoxy, hydroxy, aryl, phenyl, and OCOCR₁₃R₁₄F₁₅,wherein R₁₃, R₁₄, and R₁₅ are independently selected from the groupconsisting of H, straight, branched, or cyclic alkyl, halide, thioalkyl,thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino,hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido,carboalkoxy, acyl, sulfonyl, cyano, and nitro.
 22. The organicphotosensitive optoelectronic device of claim 16, wherein thesubphthalocyanine compound is an oligomer.
 23. The organicphotosensitive optoelectronic device of claim 1, wherein theacceptor-like material comprises a subporphyrin compound.
 24. Theorganic photosensitive optoelectronic device of claim 23, wherein thesubporphyrin compound is of the formula

wherein R₁ to R₁₂, M, and X are each selected independently, at leastone of R₁ to R₁₂ is electron donating or electron withdrawing, and theremaining R₁ to R₁₂ are independently selected from the group consistingof H, straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl,arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy,alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy,acyl, sulfonyl, cyano, and nitro, and any of R₁ to R₁₂ that are adjacentcan be part of a fused aliphatic or aromatic ring, wherein the ring maycontain one or more atoms other than carbon, M is boron, a divalentmetal, or a trivalent metal, X is an anionic group, and Z is N, CH,CR₁₆, wherein R₁₆ is selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro.
 25. The organic photosensitive optoelectronic deviceof claim 23, wherein the subporphyrin compound is of the formula

wherein R₁ to R₁₂, M, and X are each selected independently, R₁ to R₁₂are independently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro, and any of R₁ to R₁₂ that are adjacent can be part ofa fused aliphatic or aromatic ring, wherein the ring may contain one ormore atoms other than carbon, M is boron, a divalent metal, or atrivalent metal, X is an anionic group, and Z is N, CH, CR₁₆, whereinR₁₆ is selected from the group consisting of H, straight, branched, orcyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl,amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy,phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, andnitro.
 26. The organic photosensitive optoelectronic device of claim 23,wherein the subporphyrin compound is an oligomer.
 27. The organicphotosensitive optoelectronic device of claim 1, wherein the donor-likematerial comprises a subporphyrazine compound.
 28. The organicphotosensitive optoelectronic device of claim 27, wherein thesubporphyrazine compound is of formula:

wherein R₁ to R₆, M, X, and Z are each selected independently, at leastone of R₁ to R₁₂ is electron donating or electron withdrawing, and theremaining R₁ to R₆ are selected from the group consisting of H,straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl,arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy,alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy,acyl, sulfonyl, cyano, and nitro, M boron, a divalent metal, or atrivalent metal, and X is an anionic group, and Z is N, CH, CR₁₆,wherein R₁₆ is selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro.
 29. The organic photosensitive optoelectronic deviceof claim 27, wherein the subporphyrazine compound is of formula:

wherein R₁ to R₆, M, X, and Z are each selected independently, R₁ to R₆are selected from the group consisting of H, straight, branched, orcyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl,amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy,phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, andnitro, M boron, a divalent metal, or a trivalent metal, and X is ananionic group, and Z is N, CH, CR₁₆, wherein R₁₆ is selected from thegroup consisting of H, straight, branched, or cyclic alkyl, halide,thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino,arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy,carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.
 30. Theorganic photosensitive optoelectronic device of claim 29, wherein M isselected from the group consisting of B, Be, Mg, Al, and Ga, and X isselected from the group consisting of halide, alkoxy, phenoxy, hydroxy,aryl, phenyl, and OCOCR₁₃R₁₄R₁₅, wherein R₁₃, R₁₄, and R₁₅ areindependently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro.
 31. The organic photosensitive optoelectronic deviceof claim 1, wherein the acceptor-like material comprises asubporphyrazine compound.
 32. The organic photosensitive optoelectronicdevice of claim 31, wherein the subporphyrazine compound is of formula:

wherein R₁ to R₆, M, X, and Z are each selected independently, at leastone of R₁ to R₁₂ is electron donating or electron withdrawing, and theremaining R₁ to R₆ are selected from the group consisting of H,straight, branched, or cyclic alkyl, halide, thioalkyl, thioaryl,arylsulfonyl, alkylsufonyl, amino, alkylamino, arylamino, hydroxy,alkoxy, acylamino, acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy,acyl, sulfonyl, cyano, and nitro, M boron, a divalent metal, or atrivalent metal, and X is an anionic group, and Z is N, CH, CR₁₆,wherein R₁₆ is selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro.
 33. The organic photosensitive optoelectronic deviceof claim 31, wherein the subporphyrazine compound is of formula:

wherein R₁ to R₆, M, X, and Z are each selected independently, R₁ to R₆are selected from the group consisting of H, straight, branched, orcyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl,amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino, acyloxy,phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, andnitro, M boron, a divalent metal, or a trivalent metal, and X is ananionic group, and Z is N, CH, CR₁₆, wherein R₁₆ is selected from thegroup consisting of H, straight, branched, or cyclic alkyl, halide,thioalkyl, thioaryl, arylsulfonyl, alkylsufonyl, amino, alkylamino,arylamino, hydroxy, alkoxy, acylamino, acyloxy, phenyl, carboxy,carboxoamido, carboalkoxy, acyl, sulfonyl, cyano, and nitro.
 34. Theorganic photosensitive optoelectronic device of claim 33, wherein M isselected from the group consisting of B, Be, Mg, Al, and Ga, and X isselected from the group consisting of halide, alkoxy, phenoxy, hydroxy,aryl, phenyl, and OCOCR₁₃R₁₄R₁₅, wherein R₁₃, R₁₄, and R₁₅ areindependently selected from the group consisting of H, straight,branched, or cyclic alkyl, halide, thioalkyl, thioaryl, arylsulfonyl,alkylsufonyl, amino, alkylamino, arylamino, hydroxy, alkoxy, acylamino,acyloxy, phenyl, carboxy, carboxoamido, carboalkoxy, acyl, sulfonyl,cyano, and nitro.
 35. The organic photosensitive optoelectronic deviceof claim 1, wherein the device is a solar cell, photodetector, orphotosensor.
 36. The organic photosensitive optoelectronic device ofclaim 1, wherein the device is a visible spectrum photodetector orphotosensor.
 37. The organic photosensitive optoelectronic device ofclaim 1, wherein the heterojunction is a double heterostructure.
 38. Theorganic photosensitive optoelectronic device of claim 1, wherein theheterojunction is a bulk heterojunction.
 39. The organic photosensitiveoptoelectronic device of claim 1, wherein the heterojunction is a planarheterojunction.
 40. A method of preparing a heterojunction, wherein theheterojunction comprises a donor-like material and an acceptor-likematerial, the method comprising: selecting a donor-like material havinga LUMO and a HOMO, selecting a subphthalocyanine or a subporphyrinmaterial, substituted with at least one electron withdrawing or electrondonating substituent group, wherein the substituent group modulates thesubphthalocyanine or subporphyrin material LUMO and HOMO, such that thesubphthalocyanine or subporphyrin material is an acceptor-like materialfor the donor-like material, and forming a heterojunction from thedonor-like and acceptor like materials; or selecting an acceptor-likematerial, selecting a subphthalocyanine, subporphyrin, orsubporphyrazine material, substituted with at least one electronwithdrawing or electron donating substituent group, wherein thesubstituent group modulates the subphthalocyanine, subporphyrin, orsubporphyrazine material LUMO and HOMO, such that the subphthalocyanine,subporphyrin, or subporphyrazine material is a donor-like material forthe acceptor-like material, and forming a heterojunction from thedonor-like and acceptor like materials.
 41. The organic photosensitiveoptoelectronic device of claim 1, wherein the donor-like materialcomprises a subphthalocyanine compound, and the acceptor-like materialcomprises a subphthalocyanine compound.